DD152898A5 - INSECTICIDE COMPOSITION - Google Patents

Abstract

There are provided novel specifically substituted methyl ethers of ketoximes in which part of the ketoxime is phenyl substituted by nitro, trifluoromethylthio, difluoromethylthio, 2,2-difluoromethylenedioxy, trifluoromethoxy, difluoromethoxy, haloalkoxy or sulfonamido and the other part is alkyl, the substituents such as Halogen, hydroxy, alkoxy, alkylthio, alkylsulfonyl, nitro, carbalkoxy, acyl, or cyano. The invention is described to control insects with these compounds and insecticidal compositions containing the compounds and a suitable carrier substance.

Description

Berlin, January 23, 1981 58 096 12

Insecticidal composition

Field of application of the invention

The invention relates to an insecticidal composition containing new ketoxime ethers. These compounds have the general structure

Ar. _

-NOQ,

wherein Ar, R and Q are defined below.

The insecticidal compositions of the invention are used, for example, for pest control in agricultural crops.

Characteristic of the known technical solutions

U.S. Patent 3,980,799 discloses compounds of the formula:

GR ₂

as synergists for insecticides and acaricides, wherein X _{n is} halogen, alkyl, methylnioxy, etc., R _{1 is} C ₁ to C ₄ alkyl and R _{2 is} hydrogen or halogen.

In GB-PS 960 24-1, compounds of the formula:

2 2 A O 2 O

ΓΙ

τη ·

Γ)

^l .1

as synergists for insecticides, wherein X is hydrogen, n-propyl or alkyl, E ^ is hydrogen, C 1 -C 4 -alkyl or phenyl and Ep is alkyl, alkenyl, aralkyl or cycloalkyl.

In US Pat. No. 4,079 of the formula:

discloses that Benzyioximäther

^ 0

f \

= U

wherein η is 0.1 or 2, X is halogen or alkyl or alkoxy with

1 to 3 carbon atoms. And E is alkyl or alkenyl with

2 to 7 carbon atoms, optionally substituted by 1 or more halogen atoms or cyclopropyl, optionally substituted by one to four methyl groups and 1 or 2 halogen atoms, have useful insecticidal properties.

Object of the invention

The aim of the invention is to provide novel compositions with improved insecticidal activity,

Explanation of the essence of the invention

The invention has for its object to find new compounds with higher insecticidal activity, which are suitable as active ingredient in insecticidal compositions.

224 O 20

According to the invention in the new insecticidal composition as the active ingredient is a compound of the formula:

where Ar is phenyl substituted at the 2 to 6 position with nitro, irifluoromethylthio, difluoromethylthio, 2,2-lifluorinatedethylenedioxy, trifluoromethoxy, difluoromethoxy, haloalkoxy or sulfonamido; RC ₂ - to Cg alkyl, Cobis Cg-cycloalkyl or C ₂ - to C ^ -alkenyl, each of which may be substituted by halogen, hydroxy, alkoxy, alkylthio, alkylsulfonyl, cyano, nitro, Karboalkoxy or acyl; and Q is:

CH

or

wherein X is oxygen or sulfur; D is hydrogen, cyano, thiocarboxamidoalkyl or ethynyl; R ^. and Rp are the same or different and denote hydrogen, halogen, alkyl, alkenyl, alkynyl, methylenedioxy, haloalkyl, haloalkenyl or cyano; Ro is hydrogen or -ZY, wherein Z is oxygen, sulfur or methylene and Y is hydrogen, alkyl, alkenyl, alkynyl or phenyl, substitutable by alkyl, alkenyl, alkoxy, chlorine, bromine or fluorine; or

22 A 020

wherein R 1 represents hydrogen or methyl; R 1 and R 2 are the same or different and are hydrogen or alkyl and R 1 is thienyl, ethynyl or butadienyl; or

, : ^R 8 ^CH 2- »

wherein Rg is phthalimido, di- or tetrahydrophthalimide or cyano; or -

CHpC = :. CH - CHp - y wherein R _{0 is} hydrogen, halogen or methyl; or

"- C

C -

Typical examples of the Q substituent are:

CH.

O.

- <o

-CH

CH,

Ch-U

C Chi

-CH;

CHO

CH ₃

CH,

ζ · *

ι ι

-ChLC-

CF,

- CM.

-CU.

a et

CL

CL

Jei..opj.ele the β ^ '^ Ιη ^ Λνη ^ β ^ βιώΓίΘη the iol ^ e ^ clen .j trii'ztiirforgel

CH ₃ CH ₁

-ν

CF ₃ -S

CH ₃ / V -

Furthermore, the following compounds have been used as the insecticidally active component in the inventive compound compositions:

-0

The compounds of the invention have a significant biological effect. They are "particularly effective pesticides when used to control important agricultural-chitonal pests." These compounds can be used variously to achieve the biological effect and can be used per se, as a solid or in vaporized fora but preferably used as toxic components in pesticidal compositions of the compound and a carrier The compositions may be used as dusts, liquid sprays or gas-powered sprays and may contain, in addition to a carrier additive, additives such as emulsifier, wetting agent, binder, Gases that have been compressed into liquids, odorants, stabilizers, and the like. Ä., Included. 3ine variety of liquid and solid carrier over

24020

can be used in the pesticidal compositions. Non-limiting examples of liquid vehicles include water, organic solvents such as alcohols, ketones, amides, and esters, mineral oils such as kerosenes, light and medium oils, and vegetable oils such as bovine oil. Nonlimiting examples of solid repellents include talc, bentonite, diatomaceous earth, phosphophyllite, fuller's earth, gypsum, cottonseed and nutshell flours, and

AQ

'-fr - 224 0 2

various natural and synthetic clays that have a pH that does not exceed 9.5.

The amount of compounds of the invention used in pesticidal compositions has a fairly wide field of variation. It is somewhat dependent on the type of composition in which the substance is used, the nature of the state to be controlled and the method of application (i.e., spraying, dusting, etc.). In the final pesticidal composition - as it is used - pesticidal concentrations of 0.0001% by weight of the total composition can be used. In general, compositions containing about 0.05% by weight of pesticide in a liquid or solid vehicle give excellent results. In some cases, however, larger dosages of up to 10% by weight may be required.

In practice, pesticidal compositions are normally prepared in the form of concentrates, which are diluted in use until the desired concentration is obtained. For example, the concentrate may be a surface-active powder containing large amounts of the compound of the invention, a vehicle (e.g., attapulgite or other clay), and wetting agents and dispersants. Such powders may be diluted by dispersion in water prior to use to obtain a sprayable slurry containing the desired pesticide concentration for the application. Other concentrates may be solutions that can be diluted later, e.g. With kerosene. Thus, it is intended by this invention to provide pesticidal compositions containing up to about 80% by weight of the composition of a pesticidal compound of this invention. Depending on whether they are ready for use or in concentrated form, the pesticidal compositions contain

- ί - 224 0

between about 0.0001 and about 80% by weight of the compositions of a pesticidal compound of this invention and a vehicle, liquid or solid, as defined above. ,

Embodiment - ......

The invention is explained in more detail below with reference to some examples.

Synthesis proceed . , ·

In general, the compounds of this invention are prepared by two methods:

(a) Condensation of an arylalkylketoxime with an alkyl halide in the presence of a base and a suitable solvent (general procedure E).

(b) condensation of an isolated alkali metal ketoximate salt with an alkyl halide in a suitable solvent (general method F).

The ketoximes are prepared from arylalkyl ketones and hydroxylamine hydrochloride in a manner familiar to those skilled in the art, prepared according to general procedure D.

The arylalkyl ketones are obtained from commercial sources or are synthesized from available aromatic hydrocarbons and carboxylic acid chlorides or from a benzonitrile and a Grignard reagent as described in general procedures A, B and C.

The alkyl halides are obtained from commercial sources or are prepared from available alcohol and a halogenie.

4% _A

-1 = «- 22 ^ O 2 O

agent (eg, thionyl chloride, phosphorus tribromide, etc.) in a manner known to those skilled in the art.

In general a method for Afylalky A! Ketone A solution of 3.0 mole of the substituted Benzols.und 0.8 mol of alkyl acid chloride is cooled to -5 ⁰ C. Aluminum chloride (0.9 mol) is added under vigorous stirring in certain amounts, the Heaktionstemperatur is maintained at 0 ⁰ C. The reaction mixture is warmed to room temperature and stirred overnight, then the whole is added to 450 ml of concentrated hydrogen chloride and 1200 ml of sis water. The aqueous mixture is extracted twice with 350 ml portions of CH 2 Cl 2. The combined. The organic extracts are washed with 5% sodium hydroxide, H ₂ O, over MgSO / j. The residue is distilled in a short path to obtain 0.64 to 0.68 moles of the pure product.

General Procedure B for Arylalkyl Ketones Typical Example. _.- ·. , .. Preparation of 5-bromo-2-isobutyrothiophenone A solution of 8.2 g (50 mol) of 2-bromothiophene and 5.3 g (50 mol) of isobutyryl chloride in 40 ml of CS ₂ is cooled to ⁰ ° C. Aluminum chloride (7.3 g, -55 mol) is added gradually with vigorous stirring, keeping the reaction temperature at ⁰ ° C. The procedure is as in procedure A to obtain 6.2 g of the pure product. Boiling point: 70 ^° C (0.02 mm); IR (unmixed) (cnf ^1): 1666 (s), 1527 (s), 1412 (s), 1222 (s), 980 (s) NMR _(CDCl3) (ppm): 1.17 (6H, d) 3.33 (1H, m), 7.13 to .. 7.60 (2H, m).

-ίτ- 224020

Preparation of m-cooled Methylisobutyrophenon A solution of 23,4- g (0.2 mol) of m-methylbenzonitrile in 50 ml of dry tetrahydrofuran wird.auf 10 ⁰ C: General procedure C for aryl alkyl typical example ...... A 2.2 in solution (90ml, 0.2 mole) of isopropyl magnesium chloride in ether is added dropwise, keeping the reaction temperature below 30 ⁰ C muß.Der ether is removed (by distillation) and the reaction mixture is 4 Stunden 'to 70 ⁰ C heated. On cooling to room temperature, 100 ml of the aqueous 6 η HCl are added dropwise. The reaction mixture is refluxed for two hours. The resulting two layers are separated, and the aqueous layer is extracted three times with 200 ml portions of ether. The combined extracts are washed once with H 2 O, dried over MgSO 4 and compressed under reduced pressure. The residue is distilled using a "Vigreux" column to give 23.6 g (73 % yield) of the pure product.

General procedure D for ketone oximes

In general, the arylalkyl ketones prepared in general procedures A, B and C were dissolved in ethanol and refluxed for 3 to 5 hours in the presence of excess excess of hydroxylamine hydrochloride and potassium hydroxide. The reaction mixture, the oxime or its potassium hydroxide are concentrated. The reaction mixture is concentrated, and the oxime or its potassium salt is extracted with an organic solvent or HpO and then acidified with concentrated HCl. Thereafter, recrystallization was from hexane, hexane / CEC1 ₂ or EtOH / HpO.

- «- 22402ο

General Procedure E for oximinoethers

In general, 0.02 mole of ketone oxime prepared by General Procedure D was dissolved in 10 ml of toluene and added dropwise to a slurry of 0.02 mole NaH (57% mineral oil) in 10 ml toluene and 4 ml DMF. The mixture is heated to 50 ^° C until hydrogen evolution ceases, then 0.02 mole of alkyl halide is added dropwise at 30 ^° C. The reaction mixture is stirred at room temperature overnight and rapidly cooled by the addition of 50 ml of H ₂ O and 100 ml of toluene. The organic layer is washed with 5 _{tons of} 50 % aqueous NaOH and then with H 2 O then dried over MgSO 4 and concentrated under reduced pressure to give 0.015-0.017 moles of the pure product. Chromatography on silica gel using 50; 50 CH ₂ Cl ₂ / hexane as the eluent provides a high purity product. ,

General Procedure F for oximinoethers

A solution of 0.02 mole of ketoxime in 20 ml of ethanol is added to a freshly prepared ethanolic solution of 0.02 mole of NaOEt. added. The mixture is stirred at room temperature for 30 minutes and evaporated to dryness under reduced pressure. The resulting sodium oxime salt is dissolved in a minimum volume of 90 % DLiF and 10 % t-butanol, after which 0.02 mole of alkyl halide (neat) is added dropwise, causing a temperature increase of 8 ^° C. The reaction mixture is stirred overnight at room temperature and poured into HpO. The resulting oil is extracted twice in toluene. The combined organic layers are washed with 5% NaOH (50: ₂ 0 / ethanol 50 H) H ₂ O, dried over MgSO ₄ and concentrated under reduced pressure to 0.15 to 0.19 moles of> 90% of Eeinproduktes to achieve.

- 22402o

The oxime function of the compounds of this invention provides the possibility of two geometric isomers. This is shown in the following isomeric structures of a typical compound of this invention:

OH

OPh

The 0- (m-phenoxy) benzyl can either be on the isopropyl group (E or "syn" isomer) or on the p-trifluoromethoxyphenyl ring (Z or ⁿ anti ⁿ isomer). Many compounds of this type occur as mixtures of isomers. In general, E-isomer compounds or mixtures - which have many E-isoic compounds - exhibit greater activity against some insect species and may be preferred. However, Z-isomer compounds or mixtures containing many Z-isomer compounds have significant insecticidal activity. On the contrary, compounds having both isomeric structures of this invention are considered regardless of the isomeric or isomeric content in isomeric mixtures.

The following compounds were prepared:

example

From

22 A Q 2 O

m-Methylisobutyrophenon was nitrided at a temperature of about ^{0 0} C mit.einer mixture of nitric acid and sulfuric acid. The product was separated from the reaction mixture by pouring the mixture into ice-water and cooling in an ice / salt bath, allowing the oil product to solidify and filter off. The nitrated product, J-methyl-1-methylisobutyrophenone, was essentially pure.

The ketoxime was prepared by general procedure D above from the ketone, the oxime was converted to the ketoxime ether by the general procedure E above, the product having an E / Z ratio of 50:50; IH (lambda, max), cm " ¹ : 1585 (s), 1525 (s), 134-5.

Example 2

GH

N 0

m-Nitroisobutyrophenone was prepared by the reaction between p-nitrobenzopropyl chloride and the appropriate snamine (N-isobutenylmorpholine).

3 "69 g of p-nitrobenzoyl chloride was added at 5 ⁰ G dropwise to a solution des.Enamins (2.8 g) in tetrahydrofuran. After refluxing for 2 hours, the mixture was cooled to room temperature, to which diethyl ether was added. The insoluble salts were filtered off and then dissolved in water, then diethyl ether was added. After being stirred for 2 hours, the organic layer was separated and the aqueous layer was washed several times with diethyl ether, after which the ether extracts

22 A O 2 O

The crude reaction material (2.6 g) was then treated with 5 ml of concentrated hydrogen chloride and 10 ml of water and stirred overnight at room temperature, then the mixture was diluted with ether and poured into water. The ether layer was separated and combined with an ether extract of the aqueous layer. After washing and drying, the ether was removed to give the product m-nitroisobutyrophenone (1.8 g), mp 49 ⁰ G ₁ .

The ketoxime was then prepared from the ketone by General Procedure D above, the ketoximino ether formed by General Procedure E above, with the product having an E / Z ratio of 50:50. IE (lambda, max), -

1585 (s), 1520 (s), 1 ^ 90 (s), 134-5 (s).

Example 3

- 0

p-Trifluoromethoxybenzonitrile was prepared by the reaction of triphenylphosphine with p-trifluoromethoxybenzamide. This production was made after l'isaku Yamato and Shigehiko Sugasawa: Tetrahedron Letters, no. 50, p. 4383 to 4384, 1970, "Preparation of Nitrile from Primary Amide". It was chosen because it is a mild dehydration process that should not cause cleavage of the -OCiV group.

13.8 g. Triphenylphosphine was partially dissolved in 40 ml. 5.0 g of p-trifluoromethoxybenzamide was added dropwise, which was dissolved in 40 ml of dry THP. In the literature, a slight temperature

224020

ascended, which is not observed here; has been. The entire mixture was then heated to 50-60 for two hours. The solution first cloudy and then completely colorless. After et ^ Yes 30 min. a fine white precipitate was observed to be the triphenyl phosphite oxide. The product was filtered, the filtrate was distilled.

Using general procedure C above, the p-trifluoromethoxybenzonitrile was reacted with isopropyl magnesium chloride to produce the corresponding ketone. The ketcime was then prepared by the general method D from the ketone, the ketoxime was converted by the general method E into the ketoximino ether. IR (lambda, max), cm "" ¹ : 1585 cs), 14-92 (s), 1215, 1250 (wide, s).

Example 4-

p-Trifluoromethoxybenzonitrile was prepared as described in Example 3 above and reacted with cyclopropylmagnesium bromide according to General Method C to produce the ketone, which was then converted to the ketoximino ether by General Methods D and E, thereby obtaining a product a B / Z ratio of 70:30, IR (lambda, max), cm " ¹ : 1585 (s), 1492 <s), 1215, 1250 (broad, s).

4 a. * »U 4 U

example

P ₀ HCO

p-Hydroxyisobutyrophenone was prepared by the reaction of phenol (9.4 g) with isobutyric acid (17.6 g) in the presence of boron trifluoride, prepared by mixing the phenol and the acid in a 3-necked flask containing a gas dispersion tube, a stirrer and a thermometer, rose in bubbles. The temperature of the mixture was kept at less than 5 ⁰ C, and after the addition of boron trifluoride in 1.5 hours, the mixture was warmed to room temperature and then heated for 2 hours at 70 ⁰ C, then allowed to cool. After cooling to 0 ⁰ C were added 125 ml of v / ater was added dropwise, and the oily product was extracted twice into diethyl ether. The ether extracts were washed three times with 5% sodium bicarbonate and the oily product was separated.

p-Difluoromethoxyisobutyrophenone was prepared by reaction with difluorochloromethane in the presence of sodium hydroxide from the oily product. The oily product (5.0 S) dissolved in 25 mL of dioxane was placed in a 3-necked flask equipped with a gas inlet, gas outlet, magnetic stirrer, and a thermometer. This was done together with sodium hydroxide (6.0 g) dissolved in 20 ml of water, the mixture was heated to 70 ^° C., thereby raising a chlorodifluoromethane flow through the mixture, causing a temperature increase of 5 ^° C. The gaseous halocarbon was 30 min. added

- * - 224020

Thereafter, the heatshing mixture was cooled to room temperature and the top layer separated and combined with the ether layers of the base layer. The organic layers were washed with brine and water, dried and evaporated. The result was a dark brown liquid (4.3 g). The crude product was distilled at 80 to 90 ⁰ C and 53.3 Pa on diatomaceous earth, and 3.5 g of pure product were obtained.

The oxime was prepared by the general procedure D from the ketone, the oxime ether was recovered from the oxime by the general procedure E. IR (lambda, max), cm ^-1 : .1585-Cs), 1 ^ 92 (s), 1215, 1250 (broad, s), 100% E isomer.

In ecti aide Investigations Procedure Bait experiment Housefly (adult) Treatment procedure

1 ml of an aqueous suspension solution of the test compound is pipetted into a Petri dish (9 cm) containing filter paper and 0.1 g of granulated sugar. Ten adult flies were held in the shell, the shell was capped.

Results

After 24 to 75 hours the flies died. Compounds causing 90% mortality are re-determined in secondary experiments at lower concentrations. The effect can be achieved by feeding poison, contact or steam.

-49- 224 0 20

Larvicide / growth test

(Gelbfiebermückanlarven)

treatment methods

The cultured medium is treated before infestation. In mosquito larvae, 10 ml of water containing 10 ppm of the test compounds are applied in a plastic cup. After infestation with 5 larvae in the last stage, feed is added.

Results

Mortality (larvicide) is detected after 24 hours.

! Feed poison - leaf dip test Primary filter

Southern armyworm (larva) Mexican ladybird (larva)

treatment methods

Lima bean leaves of uniform size are briefly dipped in 500 ppm water-acetone of the test material. The treated leaves are placed on moistened filter paper in a Petri dish (9 cm), allowed to air dry and then infested. The trays are then closed.

Results

72. hours after the infestation was found, the mortality. Compounds active at 500 ppm are retested at 100 and 10 ppm.

224020

All test results are recorded as percent mortality, in the table the insect species are abbreviated as: Housefly (HP), Mexican Ladybug (MB), Southern Army Worm (SA) and Yellow Fever Mosquito YF).

The insecticide test described above was carried out on the compounds of Examples 1 to 5. The experimental concentrations and results are set forth in the following table:

tab Hurry MB SA CONNECTION RATE (ppm) HP 100 70 example 1 500 20 100 15 100 5 55 - 10 0 100 100 Example 2 500 100 ' 100 80 100 85 55 5 10 35. - 100 100 Example 3 500 100 100 100 100 100 100 95 10 50 100 100 Example 4 500 100 100 100 100 100 100 100 10 100 100 100 Example 5 100 100 85 0 10 95 75 5 65

Claims (9)

Invention addressed 1 »Insecticidal composition, characterized by a carrier substance and an insecticidally effective amount of a compound of the formula: wherein Ar is phenyl substituted at the 2 to 6 position with nitro, trifluoromethylthio, difluoromethylthio, 2,2-difluoromethylenedioxy, trifluoromethoxy, difluoromethoxy, haloalkoxy or sulfonamides; RC ₂ - to Cg alkyl, C ^ - to Cg-cycloalkyl or C ₂ - to C ₆ -alkenyl, each of which may be substituted by halogen, hydroxy, alkoxy, alkylthio, alkylsulfonyl, cyano, nitro, acyl or Earboalkoxy. kanni and Q CH or ^R 2 wherein X is oxygen or sulfur, D is hydrogen, cyano, thiocarboxamido, alkyl or ethynyl; R ^ and R _{2 are the} same or different and are hydrogen, halogen, alkyl, alkenyl, alkynyl, methylenedioxy, haloalkyl, haloalkenyl or Zyano and R is hydrogen or -ZY, wherein Z is oxygen, sulfur or methylene and Y is hydrogen, alkyl, alkenyl, alkynyl or phenyl, substitutable by alkyl, alkenyl, alkoxy, chlorine, bromine or 224020 Flour; or wherein R 1 is hydrogen or methyl; R ₁ and R 9 are the same or different and are hydrogen or alkyl and R _{1 is} -, atynyl, ethynyl or butadienyl; or RgCH ₂ - means wherein Rg is phthalimido, di- or tetrahydrophthalic.do or cyano; or - CH- wherein Rq is hydrogen, halogen or methyl; or is. 2. Composition according to item 1, characterized by an insecticidally effective amount of a compound of the formula: 45 · 224020 3 # Composition according to item 1, characterized by an insecticidally effective amount of a compound of the formula: CF ₃ O O. Composition according to item 1, characterized by an insecticidally effective amount of a compound of the formula: 22 40 2 O 5. Composition according to item 1, characterized by an insecticidally effective amount of a compound of the formula: - CH F ₂ HCO 6. Composition according to item 1, characterized by an insecticidally effective amount of a compound of the formula: 7. A method for controlling insects, characterized in that they are brought into contact with an insecticidally effective amount of a compound according to item 1. 8. A method for controlling insects, characterized in that they are brought into contact with an insecticidally effective amount of a compound according to item 2. 9. A method for controlling insects, characterized in that they are brought into contact with an insecticidally effective amount of a compound according to item 3, f. 224G2Ö A method of controlling insects, characterized by being contacted with an insecticidally effective amount of a compound according to item 4. 11. A method for controlling insects, characterized in that they are brought into contact with an insecticidally effective amount of a compound according to item 5. 12. A method for controlling insects, characterized in that they are brought into contact with an insecticidally effective amount of a compound according to item 6.